WO1999011614A1 - Procede de production de caprolactame - Google Patents

Procede de production de caprolactame Download PDF

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Publication number
WO1999011614A1
WO1999011614A1 PCT/EP1998/005336 EP9805336W WO9911614A1 WO 1999011614 A1 WO1999011614 A1 WO 1999011614A1 EP 9805336 W EP9805336 W EP 9805336W WO 9911614 A1 WO9911614 A1 WO 9911614A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide
acid
water
catalyst
molding
Prior art date
Application number
PCT/EP1998/005336
Other languages
German (de)
English (en)
Inventor
Eberhard Fuchs
Klemens Flick
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to IDW20000387D priority Critical patent/ID23663A/id
Priority to BR9811432-8A priority patent/BR9811432A/pt
Priority to US09/486,642 priority patent/US6218535B1/en
Priority to KR1020007002193A priority patent/KR100545610B1/ko
Priority to AU94363/98A priority patent/AU9436398A/en
Priority to EP98947446A priority patent/EP1015425B1/fr
Priority to CA002302440A priority patent/CA2302440A1/fr
Priority to JP2000508654A priority patent/JP4479871B2/ja
Priority to DE59804919T priority patent/DE59804919D1/de
Publication of WO1999011614A1 publication Critical patent/WO1999011614A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • C07D201/08—Preparation of lactams from carboxylic acids or derivatives thereof, e.g. hydroxy carboxylic acids, lactones or nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D223/08—Oxygen atoms
    • C07D223/10—Oxygen atoms attached in position 2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a new process for the preparation of cyclic lactams by reacting aminocarbonitriles with water in the presence of catalysts.
  • the catalyst consists of moldings which can be obtained by molding the oxide to give moldings and treating the oxide before or after molding with 0.1 to 30% by weight, based on the oxide of an acid, in which is sparingly soluble in the oxide.
  • the starting materials in the process according to the invention are aminocarbonitriles, preferably those of the general formula I.
  • n and m can each have the values 0, 1, 2, 3, 4, 5, 6, 7, 8 and 9 and the sum of n + m is at least 3, preferably at least 4.
  • R 1 and R 2 can in principle be substituents of any kind, it should only be ensured that the desired cyclization reaction is not influenced by the substituents.
  • R 1 and R 2 are independently dC ⁇ alkyl or C 5 -C cycloalkyl groups or C 6 -C ⁇ aryl groups.
  • Particularly preferred starting compounds are aminocarboxylic acid nitriles of the general formula
  • m has a value of 3, 4, 5 or 6, in particular 5.
  • the starting compound is 6-aminocaproic acid nitrile.
  • the reaction is carried out in the liquid phase at temperatures of generally 140 to 320 ° C, preferably 160 to 280 ° C; the pressure is generally in the range from 1 to 250 bar, preferably from 5 to 150 bar, care being taken that the reaction mixture is predominantly liquid under the conditions used.
  • the residence times are generally in the range from 1 to 120, preferably 1 to 90 and especially 1 to 60 min. In some cases, dwell times of 1 to 10 minutes have proven to be completely sufficient.
  • At least 0.01 mol, preferably 0.1 to 20 and in particular 1 to 5 mol, of water are used per mol of aminocarbonitrile.
  • the aminocarbonitrile is advantageously in the form of a 1 to 50% by weight, in particular 5 to 50% by weight, particularly preferably 5 to 30% by weight solution in water (in which case the solvent is also the reactant) or used in water / solvent mixtures.
  • solvents are alkanols such as methanol, ethanol, n- and i-propanol, n-, i- and t-butanol and polyols such as diethylene glycol and tetraethylene glycol, hydrocarbons such as petroleum ether, benzene, toluene, xylene, lactams such as pyrrolidone or caprolactam or alkyl-substituted lactams such as N-methylpyrrolidone, N-methylcaprolactam or N-ethylcaprolactam and carboxylic acid esters, preferably those of carboxylic acids having 1 to 8 carbon atoms.
  • Ammonia can also be present in the reaction.
  • Mixtures of organic solvents can of course also be used.
  • acidic, amphoteric or basic oxides can be used as catalytically active oxides, preferably aluminum oxide, such as alpha or gamma aluminum oxide, tin oxide, zinc oxide, cerium oxide, in particular titanium dioxide, amorphous, as anatase or rutile, and mixtures and phase mixtures thereof.
  • aluminum oxide such as alpha or gamma aluminum oxide, tin oxide, zinc oxide, cerium oxide, in particular titanium dioxide, amorphous, as anatase or rutile, and mixtures and phase mixtures thereof.
  • the abovementioned compounds can be combined with compounds of the 1st to 7th, in particular 2nd, 3rd or 4th main group of the periodic system, the 1st to 7th subgroup of the periodic table, the elements of the iron group or the lanthanides or actinides and mixtures of such compounds be endowed or contain them.
  • these catalysts can be up to
  • catalytically active oxides can be prepared in a manner known per se, for example by hydrolysis of the corresponding organyls, alcoholates, salts with organic or inorganic acids and subsequent annealing or calcination, and advantageously pyrogenically in particular in the case of titanium dioxide, and are generally commercially available.
  • the oxides are treated with an acid before or after molding.
  • Organic acids such as acetic acid, oxalic acid, propionic acid, butyric acid, maleic acid or inorganic acids such as isopoly acids, heteropoly acids, sulfuric acid or hydrochloric acid come as the acid.
  • Particularly suitable catalysts can be obtained by treatment with acetic acid, formic acid, nitric acid, in particular phosphoric acid or polyphosphoric acid.
  • Mixtures of acids can also be used.
  • the treatment can be carried out continuously or batchwise in one or more stages, the same acid, different acids or the same or different mixtures of acids being able to be used in the individual stages.
  • the oxides can be treated with an acid in the manner mentioned before and after molding.
  • the oxides are treated with an acid before molding.
  • 0.1 to 30, preferably 0.1 to 10, in particular 0.1 to 5% by weight of acid, calculated as pure acid, based on the pyrogenic titanium dioxide, is used.
  • the acid can be mixed with a liquid diluent such as water.
  • the oxides can be used without additives to produce the catalysts. It is also possible to add additives such as binders, for example titanium dioxide sols, salts of the oxides used, soluble titanium salt compounds, hydrolyzable titanium compounds such as titanium alcoholates or aluminum salts, such as pore formers, for example methyl cellulose, carbon fibers, organic fibers Add polymers, melamine, starch powder preferably before molding.
  • additives such as binders, for example titanium dioxide sols, salts of the oxides used, soluble titanium salt compounds, hydrolyzable titanium compounds such as titanium alcoholates or aluminum salts, such as pore formers, for example methyl cellulose, carbon fibers, organic fibers Add polymers, melamine, starch powder preferably before molding.
  • the shaped bodies can be in various forms, for example as a ball, tablet, cylinder, hollow cylinder, pellet, granulate or strand. Shaped bodies of this type can be produced in a manner known per se using appropriate molding machines such as tableting machines, extrusion molding machines, rotary granulators, pelletizers or combinations of such machines.
  • the shaped material is, if appropriate after an acid treatment, advantageously dried, in particular at temperatures from 20 to 120 ° C., preferably in an inert gas atmosphere or in air and then calcined, in particular at 400-750 ° C., 5 preferably in an inert gas atmosphere or in air
  • the heterogeneous catalysts are arranged in a fixed bed.
  • the reaction can be carried out in a manner known per se, for example in a trickle or preferably bottoms procedure, in particular continuously, by bringing the reaction mixture into contact with the catalyst bed.
  • the advantage of the process according to the invention lies in the possibility of operating the cyclization continuously in a simple manner with high yields and selectivities and short residence times with very high throughputs. Since the catalysts used have a long lifespan according to previous observations, the catalyst consumption is extremely low.
  • Example 2 Production of strands from pyrogenic titanium dioxide (phosphoric acid)
  • 11000 g of precipitated titanium dioxide powder (anatase) were kneaded with 420 g of concentrated nitric acid and 3650 g of water for 2 hours and then molded into 3 mm strands in the extrusion press with a pressure of 70 bar.
  • the strands were dried at 120 ° C. for 6 hours, then calcined at 320 ° C. for 2 hours and at 350 ° C. for a further 3 hours.
  • a solution of 6-aminocapronitrile (ACN) in water and. was introduced into a heated tubular reactor of 25 ml content (diameter 6 mm; length 800 mm), which was filled with a catalyst 1 to 4 listed in the table as grit Passed ethanol in the weight ratios given in the table.
  • the product stream leaving the reactor was analyzed by gas chromatography. The results are shown in the table as examples.
  • the product stream essentially contains ⁇ -aminocaproic acid ethyl ester and ⁇ -aminocaproic acid amide. Both can also be cyclized to caprolactam. In addition there are 5 to 8% caprolactam oligomers which can be cleaved to caprolactam.
  • the catalysts 1 to 4 have been prepared in accordance with catalyst examples 1 to 3:
  • Catalyst 1 Precipitated titanium dioxide with 3% phosphoric acid
  • Catalyst 2 Precipitated titanium dioxide with 3% phosphoric acid extruded into 3 mm strands
  • Catalyst 3 Pyrogenic titanium dioxide with 3% phosphoric acid
  • Catalyst 4 Pyrogenic titanium dioxide with 0.5% formic acid

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de lactames cycliques par réaction de nitriles d'acide aminocarboxylique avec de l'eau en phase liquide, dans un réacteur à lit fixe, en présence d'un catalyseur contenant un oxyde catalytiquement actif qui ne présente aucun constituant soluble dans les conditions de réaction. Ce procédé se caractérise en ce que le catalyseur est constitué de corps moulés qui peuvent être obtenus par moulage de l'oxyde, qui donne des corps moulés et traitement de cet oxyde, avant ou après le moulage, avec 0,1 à 30 % en poids, par rapport à l'oxyde, d'un acide dans lequel celui-ci est difficilement soluble.
PCT/EP1998/005336 1997-09-03 1998-08-21 Procede de production de caprolactame WO1999011614A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
IDW20000387D ID23663A (id) 1997-09-03 1998-08-21 Persiapan kaprolaktam
BR9811432-8A BR9811432A (pt) 1997-09-03 1998-08-21 Processo para a preparação de lactamas cìclicas
US09/486,642 US6218535B1 (en) 1997-09-03 1998-08-21 Caprolactam production process
KR1020007002193A KR100545610B1 (ko) 1997-09-03 1998-08-21 카프롤락탐의 제조 방법
AU94363/98A AU9436398A (en) 1997-09-03 1998-08-21 Caprolactam production process
EP98947446A EP1015425B1 (fr) 1997-09-03 1998-08-21 Procede de production de caprolactame
CA002302440A CA2302440A1 (fr) 1997-09-03 1998-08-21 Procede de production de caprolactame
JP2000508654A JP4479871B2 (ja) 1997-09-03 1998-08-21 カプロラクタムの製造法
DE59804919T DE59804919D1 (de) 1997-09-03 1998-08-21 Verfahren zur herstellung von caprolactam

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19738463.3 1997-09-03
DE19738463A DE19738463C2 (de) 1997-09-03 1997-09-03 Verfahren zur Herstellung von Caprolactam

Publications (1)

Publication Number Publication Date
WO1999011614A1 true WO1999011614A1 (fr) 1999-03-11

Family

ID=7841048

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/005336 WO1999011614A1 (fr) 1997-09-03 1998-08-21 Procede de production de caprolactame

Country Status (15)

Country Link
US (1) US6218535B1 (fr)
EP (1) EP1015425B1 (fr)
JP (1) JP4479871B2 (fr)
KR (1) KR100545610B1 (fr)
CN (1) CN1177820C (fr)
AR (1) AR017040A1 (fr)
AU (1) AU9436398A (fr)
BR (1) BR9811432A (fr)
CA (1) CA2302440A1 (fr)
DE (2) DE19738463C2 (fr)
ES (1) ES2181276T3 (fr)
ID (1) ID23663A (fr)
MY (1) MY120160A (fr)
TW (1) TW434226B (fr)
WO (1) WO1999011614A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1011577A3 (fr) * 1997-11-27 1999-11-09 Solvay Catalyseur d'epoxydation, son utilisation et procede d'epoxydation en presence de catalyseur.
DE10033518A1 (de) * 2000-07-11 2002-01-24 Basf Ag Verfahren zur Abtrennung von Ammoniak

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150295A2 (fr) * 1983-12-19 1985-08-07 Allied Corporation Préparation sélective d'amides N-substitués utilisant de compositions de catalyseurs de Cu(O)/oxides métalliques
US4568736A (en) * 1984-09-17 1986-02-04 The Standard Oil Company Preparation of polyamide from omega-aminonitrile with oxygen containing phosphorus catalyst
DE4339648A1 (de) * 1993-11-20 1995-05-24 Basf Ag Verfahren zur Herstellung von Caprolactam
US5495016A (en) * 1994-11-25 1996-02-27 Basf Aktiengesellschaft Preparation of caprolactam
WO1996022974A1 (fr) * 1995-01-27 1996-08-01 Rhone-Poulenc Fiber And Resin Intermediates Procede de preparation de lactame
DE19517823A1 (de) * 1995-05-18 1996-11-21 Basf Ag Verfahren zur Herstellung von Caprolactam

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19517821A1 (de) * 1995-05-18 1996-11-21 Basf Ag Verfahren zur Herstellung von Caprolactam

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150295A2 (fr) * 1983-12-19 1985-08-07 Allied Corporation Préparation sélective d'amides N-substitués utilisant de compositions de catalyseurs de Cu(O)/oxides métalliques
US4568736A (en) * 1984-09-17 1986-02-04 The Standard Oil Company Preparation of polyamide from omega-aminonitrile with oxygen containing phosphorus catalyst
DE4339648A1 (de) * 1993-11-20 1995-05-24 Basf Ag Verfahren zur Herstellung von Caprolactam
US5495016A (en) * 1994-11-25 1996-02-27 Basf Aktiengesellschaft Preparation of caprolactam
WO1996022974A1 (fr) * 1995-01-27 1996-08-01 Rhone-Poulenc Fiber And Resin Intermediates Procede de preparation de lactame
DE19517823A1 (de) * 1995-05-18 1996-11-21 Basf Ag Verfahren zur Herstellung von Caprolactam

Also Published As

Publication number Publication date
DE19738463C2 (de) 1999-09-23
CA2302440A1 (fr) 1999-03-11
KR20010023545A (ko) 2001-03-26
ID23663A (id) 2000-05-11
DE19738463A1 (de) 1999-03-04
ES2181276T3 (es) 2003-02-16
CN1177820C (zh) 2004-12-01
EP1015425A1 (fr) 2000-07-05
MY120160A (en) 2005-09-30
DE59804919D1 (de) 2002-08-29
TW434226B (en) 2001-05-16
US6218535B1 (en) 2001-04-17
CN1269789A (zh) 2000-10-11
BR9811432A (pt) 2000-08-22
AR017040A1 (es) 2001-08-22
KR100545610B1 (ko) 2006-01-25
EP1015425B1 (fr) 2002-07-24
JP4479871B2 (ja) 2010-06-09
AU9436398A (en) 1999-03-22
JP2001514250A (ja) 2001-09-11

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